Impact of molecular orbital distribution on photoelectron intensity for picene film

Highlights: • Development in the theoretical evaluation of photoelectron intensity from π-electronic states. • Experimental and computed angular distribution by DFT and multiple-scattering theory. • Characterization of the top five π-electronic states for picene (C₂₂H₁₄) film. - Abstract: The recent development in the theoretical evaluation of photoelectron intensity from π-electronic states delocalized over a molecule is discussed. By comparing the experimental photoelectron angular distribution (PAD) from the organic molecular assemblies with computed PAD we show that the use of the initial-state orbitals by density functional theory and the final continuum states by multiple-scattering theory is suited for simulations of angle-resolved photoelectron spectrum (ARPES) and PAD. We demonstrate that the ARPES and PAD simulations are useful to characterize the top five π-electronic states for picene (C₂₂H₁₄) film